JP5667404B2 - Toner composition and process - Google Patents

Description

  The present disclosure is generally directed to a toner process, and more specifically to an emulsion aggregation and coalescence process, and a toner composition formed by such a process and a development process using such toner.

  Appropriate components and processes for each of the above patents and publications can also be selected for the present compositions and processes in embodiments of the present disclosure.

  In many electrophotographic engines and processes, a toner image can be applied to a substrate. The toner can then be fixed to the substrate by heating the toner with a contact or non-contact fuser, wherein the transferred heat causes the toner mixture to melt on the substrate. In electrophotographic digital printing using current toner, various printing glosses can be generated when fixing using a contact fixing device such as a roll or belt type fixing subsystem. The desired gloss level depends on the specific customer application.

US Patent Application Publication No. 2006/0222991 US Pat. No. 5,290,654 US Pat. No. 5,302,486 U.S. Pat. No. 3,590,000 U.S. Pat. No. 3,800,588 US Pat. No. 6,214,507 US Pat. No. 5,236,629 U.S. Pat. No. 5,330,874 U.S. Pat. No. 4,225,990

  The present disclosure provides toner, a process for producing the toner, and an apparatus that utilizes such toner. In embodiments, the toner of the present disclosure can comprise at least one amorphous resin, at least one infrared absorber, at least one crystalline resin, an optional colorant, and an optional wax, wherein at least One infrared absorber has a maximum absorbance at wavelengths from about 700 nm to about 850 nm.

  In other embodiments, the toner of the present disclosure comprises at least one amorphous polyester resin, at least one infrared absorber, at least one crystalline polyester resin, an optional colorant, and an optional wax, and at least one Two infrared absorbers have maximum light absorption at wavelengths from about 700 nm to about 850 nm and do not absorb light at wavelengths from about 380 nm to about 700 nm.

  The printing apparatus of the present disclosure includes at least one heating device, a toner source, an optional contact fuser, a non-contact fuser comprising an infrared light source operating at a wavelength from about 750 nm to about 2500 nm, a substrate preheater, an image A support member preheater, and an injector, wherein the toner comprises at least one amorphous resin, at least one infrared absorber, at least one crystalline resin, an optional colorant, and an optional wax. Wherein at least one infrared absorber has a maximum absorbance at a wavelength from about 700 nm to about 850 nm and does not absorb light at a wavelength from about 380 nm to about 700 nm.

4 is a graph of a UV-vis-NIR spectrum of an infrared (IR) absorber that can be used in accordance with the present disclosure. It is a graph of the UV-vis-NIR spectrum of the non-pigmented amorphous resin of an infrared (IR) absorber. 1 is a graph of UV-vis-NIR spectra of a resin of the present disclosure including an amorphous resin and an infrared (IR) absorber.

  The present disclosure provides a toner design for non-contact fixing that produces high print gloss with short residence time. According to the present disclosure, energy absorbing materials can be included in conventional color toners to meet non-contact fusing requirements. In embodiments, an infrared (IR) absorber is added to the color toner to prevent gloss and wrinkle differences between the color toner and the black toner.

  In embodiments, the present disclosure is made by a chemical process, such as emulsion aggregation, in which the resulting toner composition comprises an unsaturated polyester resin, an IR absorber, optionally a wax, and optionally a colorant. Is directed to a curable toner composition comprising:

  The process of the present disclosure comprises an unsaturated crystalline or amorphous polymer resin such as a polyester in embodiments, an IR absorber, optionally a wax, and optionally a colorant in embodiments, in the presence of a flocculant. Aggregating particles, such as containing particles, can be included.

There are many advantages to the toners and toner compositions obtained by the processes described herein. The process is performed with narrow particles, such as from about 1.2 to about 1.25, in a size from about 2.5 microns to about 9 microns in diameter, in embodiments from about 3 microns to about 6 microns in diameter. It makes it possible to prepare particles of size distribution without using a classifier. Further, by using a crystalline resin in the toner composition, a low-temperature melting or ultra-low temperature fixing temperature can be obtained. The aforementioned low-temperature fixing temperature enables non-contact fixing. The toner composition provides other advantages such as high temperature document offset properties up to about 85 ° C., and resistance to organic solvents such as methyl ethyl ketone (MEK).
In embodiments, the toner prepared according to the present disclosure can be a low-melting EA toner that includes an unsaturated resin, an IR absorber, and a shell.

  The toner of the present disclosure can include any resin suitable for the application for forming the toner. Such resins can then be made from any suitable monomer.

In embodiments, the polymer used to form the resin can be a polyester resin.
In embodiments, the resin can be a polyester resin formed by reacting a diol with a diacid or diester in the presence of an optional catalyst.
In embodiments, unsaturated, amorphous polyester resins can be used as the resin.

  In embodiments, suitable amorphous resins for use in the toners of the present disclosure have a weight average molecular weight from about 10,000 to about 100,000, in embodiments from about 15,000 to about 30,000. Can have.

（ＩＩ）
ここで、ｂは、約５から約２０００まで、ｄは約５から約２０００までである。 Suitable crystalline resins include those disclosed in US Pat. In embodiments, a suitable crystalline resin can be composed of a mixture of ethylene glycol and dodecanedioic acid and fumaric acid comonomer having the formula:

(II)
Here, b is from about 5 to about 2000, and d is from about 5 to about 2000.

  In embodiments, suitable crystalline resins used in the toners of the present disclosure have a weight average molecular weight from about 10,000 to about 100,000, in embodiments from about 15,000 to about 30,000. be able to.

  One, two, or more resins can be used to form the toner. In embodiments using two or more resins, the resin can be, for example, from about 1% (first resin) / 99% (second resin) to about 99% (first resin) / 1. % (Second resin), in embodiments from about 10% (first resin) / 90% (second resin) to about 90% (first resin) / 10% (second resin) Any suitable ratio (eg, weight ratio) can be used.

  In embodiments, suitable toners of the present disclosure can include two amorphous polyester resins and one crystalline polyester resin.

  As described above, in the embodiment, the resin can be formed by an emulsion aggregation method. Using such a method, the resin can be present in the resin emulsion, which can then be combined with other ingredients and additives to form the toner of the present disclosure.

  The polymer resin is in an amount from about 65% to about 95%, or preferably from about 75% to about 85%, by weight of toner particles (ie, toner particles excluding external additives) on a solids basis. Can exist in

  Low acid number polymers have also been found to give better cross-linking results under irradiation.

  According to the present disclosure, at least one infrared (IR) absorber is added to the toner for non-contact fixing. The IR absorber can be added to at least one color toner, and in embodiments can be added to multiple color toners. By changing the IR absorber formulation in each color toner, it should be possible to heat the particles more uniformly between the different color toners, and also to heat the transparent particles more efficiently. it can.

  The visible region boundary of the absorption spectrum is from about 380 nm to about 700 nm, corresponding to an energy boundary from about 3.26 eV to about 1.77 eV.

  In embodiments, the IR absorber used in the toner of the present disclosure has a maximum absorbance at wavelengths from about 700 nm to about 850 nm, in embodiments from about 725 nm to about 825 nm, and in embodiments from about 730 nm to about 800 nm. Have The IR absorber used in the toner of the present disclosure may not absorb at all in the visible light region having a wavelength of about 380 nm to about 700 nm.

  The resin of the above-described resin emulsion is a polyester resin in the embodiment, and can be used to form a toner composition. Such toner compositions can include optional colorants, waxes and other additives. The toner can be formed using any method within the purview of those skilled in the art, including but not limited to emulsion aggregation methods.

  In embodiments, the colorant, wax, and other additives used to form the toner composition can be a dispersion containing a surfactant. Furthermore, the toner particles can be formed by an emulsion aggregation method, in which case the resin and other toner components including at least one IR absorber are disposed in one or more surfactants, An emulsion is formed and the toner particles are agglomerated, coalesced, optionally washed and dried, and collected.

  One, one, or more surfactants can be used. The surfactant can be selected from an ionic surfactant or a nonionic surfactant. Anionic surfactants and cationic surfactants are included in the term “ionic surfactant”. In embodiments, the surfactant is in an amount from about 0.01% to about 5% by weight of the toner composition, such as from about 0.75% to about 4% by weight of the toner composition. Can be used such that an amount from about 1% to about 3% by weight of the toner composition is present.

  For the colorant to be added, various known suitable colorants such as dyes, pigments, dye mixtures, pigment mixtures, dye and pigment mixtures, and the like can be included in the toner. The colorant is, for example, an amount from about 0.1% to about 35% by weight of the toner, or from about 1% to about 15% by weight of the toner, or from about 3% to about 10% by weight of the toner. Can be included in the toner.

  In addition to the polymer binder resin and the IR absorber, the toner of the present disclosure can also optionally contain a wax that can be a single type of wax or a mixture of two or more different waxes. . A single wax may be added to the toner formulation to identify, for example, toner particle shape, the presence and amount of wax on the toner particle surface, charging and / or fixing properties, gloss, peelability, offset properties, etc. The toner characteristics can be improved. Alternatively, a combination of waxes can be added to give the toner composition multiple properties.

  Optionally, the wax can also be combined with resins, IR absorbers, and optional UV additives in toner particle formation. When a wax is included, the wax can be present, for example, in an amount from about 1% to about 25% by weight of the toner particles, and in embodiments from about 5% to about 20% by weight of the toner particles. .

  Waxes that can be selected include, for example, waxes having a weight average molecular weight of from about 500 to about 20,000, and in embodiments from about 1,000 to about 10,000.

  The toner particles can be prepared by any method within the purview of those skilled in the art. Embodiments relating to toner particle generation are described below with respect to an emulsion aggregation process, but any suitable toner particle preparation, including chemical processes such as the suspension and encapsulation processes disclosed in US Pat. The method can be used. In embodiments, the toner composition and toner particles can be prepared by an agglomeration and fusing process, in which case small size resin particles are agglomerated to a suitable toner particle size and then fused to the final toner particles. Get shape and form.

  In embodiments, the toner composition comprises a mixture of an optional wax and any other desired or necessary additives, and an emulsion comprising the above resin and IR absorber, optionally as described above. It can be prepared by an emulsion aggregation process, such as a process comprising agglomerating in an agent and then fusing the agglomerated mixture. The mixture can be a mixture of two or more emulsions containing a resin and an IR absorber, with an optional wax or other material that can also be optionally dispersed in a surfactant. It can be prepared by adding to an emulsion. The pH of the resulting mixture can be adjusted with acids such as acetic acid, nitric acid and the like. In embodiments, the pH of the mixture can be adjusted from about 2 to about 4.5. Furthermore, in embodiments, the mixture can be homogenized. When homogenizing the mixture, homogenization can be achieved by mixing at about 600 to about 4,000 revolutions per minute.

  After preparing the above mixture, a flocculant can be added to the mixture. Any suitable flocculant can be used to form the toner. Suitable flocculants include, for example, aqueous solutions of divalent cations or polyvalent cations.

  For the mixture used to form the toner, the flocculant is, for example, from about 0.1% to about 8%, in embodiments from about 0.2% to about 5%, by weight of the resin in the mixture. It can be added in amounts up to wt%, in other embodiments from about 0.5 wt% to about 5 wt%, although this amount can be outside these ranges. This provides a sufficient amount of flocculant for aggregation.

Toner gloss can be influenced by the amount of metal ions, eg, Al ³⁺ , retained in the particles. The amount of metal ions retained can be further adjusted by adding EDTA. In embodiments, the amount of crosslinker, such as Al ³⁺ , retained in the toner particles of the present disclosure is from about 0.1 pph to about 1 pph, in embodiments from about 0.25 pph to about 0.8 pph, In embodiments, it can be about 0.5 pph.

  In order to control particle aggregation and coalescence, in embodiments, the flocculant can be added to the mixture metered over time. For example, the flocculant can be metered into the mixture over a period of about 5 minutes to about 240 minutes, in embodiments from about 30 minutes to about 200 minutes, but longer as desired or required. May be shorter. In addition, the flocculant may be added while maintaining the mixture under stirring from about 50 rpm to about 1,000 rpm in embodiments, and from about 100 rpm to about 500 rpm in other embodiments. Is below the glass transition temperature of the resin as described above, in embodiments from about 30 ° C. to about 90 ° C., in embodiments from about 35 ° C. to about 70 ° C.

  The particles can be agglomerated until a predetermined desired particle size is obtained. The predetermined desired particle size refers to the desired particle size to be obtained, determined prior to formation, and the particle size is monitored during the growth process until such particle size is reached. Samples can be taken during the growth process and analyzed for average particle size, for example, by a Coulter counter. Thus, agglomeration is carried out by maintaining a high temperature or by slowly raising the temperature, for example from about 40 ° C. to about 100 ° C., and allowing the mixture to reach this temperature for about 0.5 hours to about 6 hours. In form, it can be advanced to yield agglomerated particles by maintaining stirring for about 1 hour to about 5 hours. Once the predetermined desired particle size is reached, the growth process is stopped. In embodiments, the predetermined desired particle size can be within the above-described toner particle size range.

  Particle growth and shaping after the addition of the flocculant can be performed under any suitable conditions. For example, growth and shaping may be performed under conditions where agglomeration occurs separately from fusion. For separate aggregation and fusion stages, the aggregation process can be, for example, from about 40 ° C. to about 90 ° C., in embodiments from about 45 ° C. to about 80 ° C., which can be lower than the glass transition temperature of the resin described above. Under high temperature shearing conditions.

  In embodiments, an optional shell can be applied to the formed agglomerated toner particles. Any of the above-described resins suitable as the core resin can be used as the shell resin. The shell resin can be applied to the aggregated particles by any method within the purview of those skilled in the art. In embodiments, the shell resin can be an emulsion comprising any of the surfactants described above. The agglomerated particles described above can be combined with this emulsion so that the resin forms a shell over the formed agglomerated particles. In an embodiment, amorphous polyester can be used to form a shell on aggregated particles to form toner particles having a core-shell structure.

  The shell resin may be present in an amount from about 20% to about 30%, in embodiments from about 24% to about 28% by weight of the toner particles. In embodiments, the IR absorber described above can be included in the shell. Thus, the IR absorber can be present in the core, in the shell, or both.

  Thus, the IR absorber can be present in an amount from about 0.01% to about 5% by weight of the toner particles, and in embodiments from about 0.5% to about 2% by weight of the toner particles. .

  An emulsion of the present disclosure comprising the above-described resin and optional additives can include particles having a particle size from about 100 nm to about 260 nm, and in embodiments from about 105 nm to about 185 nm. The toner is from about 0.01% to about 2% by weight of the toner, in embodiments from about 0.10% to about 1%, in embodiments from about 0.2% to about 0.5%. It can have an IR absorber in an amount of% by weight.

  Emulsions containing these resins have from about 10% to about 25% solids by weight, in embodiments from about 12% to about 20% by weight, in embodiments from about 17% solids. It can have a solid content of wt%.

  Once the desired final particle size of the toner particles is reached, the pH of the mixture can be adjusted with a base to a value from about 6 to about 10, in embodiments from about 6.2 to about 7. Adjusting the pH can be used to freeze or stop toner growth. The substrate used to stop toner growth can include, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, combinations thereof and the like.

  Following agglomeration to the desired particle size and formation of the optional shell described above, the particles can be fused to the desired final shape, but this fusion is, for example, crystalline to prevent plasticization. Achieved by heating the mixture to a temperature from about 55 ° C. to about 100 ° C., in embodiments from about 65 ° C. to about 75 ° C., in embodiments about 70 ° C., which can be below the melting point of the resin. Is done. With the understanding that temperature is a function of the resin used in the binder, higher or lower temperatures can be used.

  Fusion can proceed and be accomplished over a time period of from about 0.1 hours to about 9 hours, in embodiments from about 0.5 hours to about 4 hours, although times outside these ranges may be used. .

  After coalescence, the mixture can be cooled to room temperature, for example from about 20 ° C to about 25 ° C. Cooling may be rapid or slow as required. A suitable cooling method includes introducing cold water into a jacket around the reactor. After cooling, the toner particles can optionally be washed with water and then dried. Drying can be performed by any suitable drying method including, for example, freeze drying.

  In embodiments, the toner particles can include other optional additives as desired or required.

  The toner particles can also be mixed with external additive particles including flow promoting additives that can be present on the surface of the toner particles. Each of these external additives can be present in an amount from about 0.1% to about 5% by weight of the toner, and in embodiments from about 0.25% to about 3%, although the amount is It may be out of range. Suitable additives include those disclosed in US Pat. Again, these additives can be added simultaneously with the shell resin described above or after application of the shell resin.

The properties of the toner particles can be determined by any suitable technique and apparatus. The volume average particle diameters D _50v , GSDv, and GSDn can be measured by means of a measuring device such as a particle size distribution measuring apparatus 3 manufactured by Beckman Coulter, which is operated according to the manufacturer's instructions. Typical sampling can be performed as follows. A small amount of toner sample of about 1 gram is obtained and filtered through a 25 micrometer sieve, then an isotonic solution is added to a concentration of about 10%, and then a particle size distribution measuring device 3 manufactured by Beckman Coulter. Call it. The toner produced according to the present disclosure has excellent charging characteristics when exposed to extreme relative humidity (RH) conditions. The low humidity zone (C zone) can be about 10 ° C./15% RH, while the high humidity zone (A zone) can be about 28 ° C./85% RH. The toner of the present disclosure also has a parent toner specific charge (Q / M) of about −3 μC / g to about −45 μC / g, and in embodiments about −10 μC / g to about −40 μC / g, and , Having a final toner charge after mixing of surface additives of about −10 μC / g to about −45 μC / g.

  The method of the present disclosure can be used to obtain a desired gloss level. Thus, for example, the gloss of the toner of the present disclosure, when measured in Gardner gloss units (ggu), is from about 20 ggu to about 100 ggu, in embodiments from about 50 ggu to about 95 ggu, and in embodiments from about 60 ggu to about about It can have a gloss of up to 90 ggu.

In embodiments, the toner of the present disclosure can be used as an ultra low temperature melting (ULM) toner. In embodiments, the dry toner particles can have the following characteristics, except for external surface additives.
(1) Volume average diameter (also referred to as “volume average particle size”) from about 2.5 microns to about 20 microns, in embodiments from about 2.75 microns to about 10 microns, in other embodiments From about 3 microns to about 9 microns.
(2) The number average geometric standard deviation (GSDn) and / or the volume average geometric standard deviation (GSDv) is from about 1.05 to about 1.55, in embodiments from about 1.1 to about 1.4. is there.
(3) The roundness is from about 0.9 to about 1, (eg, measured with a Sysmex FPIA2100 analyzer), in embodiments from about 0.93 to about 0.99, and in other embodiments about 0. 95 to about 0.98.
(4) The glass transition temperature is from about 35 ° C. to about 60 ° C., in embodiments from about 37 ° C. to about 45 ° C.
(5) The surface area of the toner particles is from about 1.3 m ² / g to about 6.5 m ² / g as measured by the known BET method. For example, for cyan, yellow, and black toner particles, the BET surface area should be less than 2 m ² / g, for example from about 1.4 m ² / g to about 1.8 m ² / g, and for magenta toner Can be from about 1.4 m ² / g to about 6.3 m ² / g.

  In embodiments, the toner particles have separate crystalline polyester and wax melting points and amorphous polyester glass transition temperatures, as measured by DSC, and the melting and glass transition temperatures are amorphous. It is desirable not to be substantially degraded by plasticization of the quality or crystalline polyester, or by IR absorbers or any optional wax. In order to achieve deplasticization, it is desirable to carry out the emulsion aggregation at a fusion temperature below the melting point of the crystalline and wax components.

  The toner particles thus formed can be blended into the developer composition. Toner particles can be mixed with carrier particles to obtain a two-component developer composition. The toner concentration in the developer can be from about 1% to about 25% by weight of the total weight of the developer, and in embodiments from about 2% to about 15% by weight of the total weight of the developer. .

  Examples of carrier particles that can be used to mix with the toner include particles that can obtain a triboelectric charge of the opposite polarity as the toner particles.

  The selected carrier particles can be used with or without a coating. In embodiments, the carrier particles can include a core having a coating thereon that can be formed from a mixture of polymers that are not so close in the charge train.

  Various effective and suitable means such as cascade roll mixing, tumbling, cutting, shaking mixing, electrostatic powder cloud spraying, fluid bed, electrostatic disk processing, electrostatic curtain, combinations thereof and the like Can be used to apply the polymer to the carrier core particles. The mixture of carrier core particles and polymer is then heated to allow the polymer to dissolve and settle to the carrier core particles. The coated carrier particles are then cooled and then sized to the desired particle size.

  In embodiments, suitable carrier bodies include, for example, steel cores having a size from about 25 μm to about 100 μm, in embodiments from about 50 μm to about 75 μm. For example, from about 0.5% to about 10%, in embodiments from about 0.7% to about 5% by weight of methyl acrylate and carbon black. It can be coated with a polymer mixture.

  The carrier particles can be mixed with the toner particles in various suitable combinations. The concentration can be from about 1% to about 20% by weight of the toner composition. However, it is also possible to obtain a developer composition having desired characteristics by using different toner and carrier ratios.

  This toner can be used in electrophotographic processes including those disclosed in Patent Document 9. In the embodiment, for example, any well-known type of image developing apparatus such as magnetic brush development, one-component jumping development, hybrid cleaning unnecessary development, and the like can be used. These and similar development systems are within the purview of those skilled in the art.

  The imaging process includes preparing an image using an electrophotographic apparatus that includes, for example, a charging element, an imaging element, a photoconductive element, a developing element, a transfer element, and a fusing element. In embodiments, the developing element can include a developer prepared by mixing a carrier with the toner composition described herein. The electrophotographic apparatus can include a high-speed printer, a monochrome high-speed printer, a color printer, and the like.

  Once the image is formed with a toner / developer by a suitable image development method, such as any one of the methods described above, the image is then transferred to an image receiving medium such as paper. In embodiments, toner can be used to develop an image in a developing device that uses a fuser roll member. The fixing roll member is a contact fixing device within the recognition of those skilled in the art, and can fix the toner to the image receiving medium using heat and pressure from the roll. In embodiments, the fuser member may also be after or during dissolution in the image receiving substrate, for example from about 70 ° C. to about 160 ° C., in embodiments from about 80 ° C. to about 150 ° C., in other embodiments. Is heated from about 90 ° C. to about 140 ° C. (although temperatures outside these ranges may be used) above the fixing temperature of the toner.

  In embodiments, the fixing of the toner image can be performed by any conventional means such as a combination of heat and pressure, such as by using a heated pressure roller. For example, the irradiation can be performed in the same fixing housing and / or step where conventional fixing is performed, or the irradiation can be performed in a separate irradiation fixing mechanism and / or step. In some embodiments, this irradiation step can result in non-contact fixing of the toner, so conventional pressure fixing can be unnecessary.

  In other embodiments, the irradiation can be performed in a fusing housing and / or step separate from the conventional fusing housing and / or step.

  In other embodiments, the toner image can be fixed by irradiation and optional heating without using conventional pressure fixing. This can be referred to as non-contact fixing in the embodiment. Irradiation fixing can be performed with any suitable irradiation device and under suitable parameters to produce the desired degree of crosslinking in the unsaturated polymer. Suitable non-contact fusing methods are within the purview of those skilled in the art and in embodiments include flash fusing, radiation fusing, and / or vapor fusing. These non-contact fixing processes do not require pressure to fix the toner. In embodiments, flash fixing can be used. In embodiments, the non-contact fusing device used by the present disclosure can include an infrared light source that operates at a wavelength of about 750 nm to about 2500 nm.

  In embodiments, non-contact fusing can cause toner to be irradiated from about 700 nm to about 850 nm, in embodiments from about 725 nm to about 845 nm in infrared light, from about 5 milliseconds to about 2 seconds, in embodiments. Is performed by exposing for a time from about 50 milliseconds to about 1 second.

  If heat is also applied, the image may be, for example, from about 100 ° C to about 250 ° C, such as from about 125 ° C to about 225 ° C, or from about 150 ° C or about 160 ° C to about 180 ° C or about 190 ° C. It can be fixed by irradiation with infrared light or the like in a heating environment.

  When radiation fixing is applied to a toner composition containing an IR absorber, the resulting fixed image does not provide document offset properties, i.e., temperatures up to about 90 ° C, such as up to about 85 ° C or about At temperatures up to 80 ° C., the image exhibits no document offset.

Example 1
Preparation of a crystalline resin emulsion comprising a crystalline polyester resin derived from dodecanedioic acid, ethylene glycol, and fumaric acid, copoly (ethylene-dodecanoate) -copoly- (ethylene-fumarate) Heating mantle, mechanical stirrer, bottom A 1 liter Parr reactor equipped with a drain valve and distillation apparatus was charged with dodecanedioic acid (about 443.6 grams), fumaric acid (about 18.6 grams), hydroquinone (about 0.2 grams), n- Butylstannic acid (FASCAT 4100) catalyst (about 0.7 grams) and ethylene glycol (about 248 grams) were charged. This material was stirred under a stream of carbon dioxide and slowly heated to about 150 ° C. over about 1 hour. The temperature was then raised to about 180 ° C. at about 15 ° C., followed by about 10 ° C. every 30 minutes. During this time, water was distilled off as a by-product. The temperature was then raised to about 195 ° C in about 5 ° C increments over about 1 hour. The pressure was then reduced to about 0.03 mbar over about 2 hours and any excess glycol was collected in the distillation receiver. Under a stream of carbon dioxide, the resin was returned to atmospheric pressure and then trimellitic anhydride (about 12.3 grams) was added. The pressure was slowly reduced to about 0.03 mbar over about 10 minutes where it was held for another 40 minutes. The crystalline resin, copoly (ethylene-dodecanoate) -copoly- (ethylene-fumarate), is returned to atmospheric pressure and then drained through the bottom drain valve to a viscosity of about 87 Pa · s (measured at about 85 ° C.), about 69 A resin having a melting onset temperature of 0 ° C., a melting point temperature peak of about 78 ° C., and a recrystallization peak on cooling of about 56 ° C. measured by a differential scanning calorimeter manufactured by DuPont was obtained. The acid value of the resin was found to be about 12 meq / KOH.

  About 816 grams of ethyl acetate was added to about 125 grams of the crystalline resin described above. The resin was dissolved on a hot plate by heating to about 65 ° C. with stirring at about 200 rpm. In a separate 4 liter glass reaction vessel, about 4.3 grams of TAYCA POWER surfactant (Taika Japan, sodium dodecylbenzenesulfonate) (about 47% aqueous solution), about 2.2 grams of weight Sodium carbonate (with an acid number of about 12 meq / KOH) and about 708.33 grams of deionized water were added. This aqueous solution was heated to about 65 ° C. with stirring at about 200 rpm on a hot plate.

  The resin dissolved in the ethyl acetate mixture was slowly poured into a 4 liter glass reactor containing the aqueous solution while homogenizing at about 4,000 rpm. The homogenizer speed was then increased to 10,000 rpm and left for about 30 minutes. The homogenized mixture was placed in a Pyrex® distillation apparatus with a heating jacket with stirring at about 200 rpm. The temperature was raised to about 80 ° C. at about 1 ° C./min. Ethyl acetate was distilled off from the mixture at about 80 ° C. for about 120 minutes. The mixture was cooled to below about 40 ° C. and then screened with a 20 micron sieve. The pH of the mixture was adjusted to about 7 using about 4% aqueous NaOH and centrifuged. The resulting resin contained about 35.1 wt% solids in water and had a volume average diameter of about 108 nanometers as measured by a HONEYWELL MICROTRAC® UPA150 particle size analyzer. .

Comparative Example 1
A transparent toner containing no IR absorber was prepared as follows. In a 2 liter beaker, about 816 grams of ethyl acetate was added to about 125 grams of amorphous polyester resin commercially available as XP777 resin from Reichold Chemicals. The resin was dissolved by heating to about 65 ° C. with stirring at about 200 rpm on a hot plate. In a separate 4 liter glass reaction vessel, about 3.05 grams (for an acid number of about 17) sodium bicarbonate was added to about 708.33 grams of deionized water. This aqueous solution was heated to about 65 ° C. with stirring at about 200 rpm on a hot plate. A 4 liter glass reactor containing this aqueous solution was slowly poured into the mixed amorphous resin and ethyl acetate mixture with homogenization at about 4,000 rpm. The homogenizer speed was then increased to about 10,000 rpm and left for about 30 minutes. The homogenized mixture was placed in a Pyrex® distillation apparatus fitted with a heating jacket with stirring at about 200 rpm. The temperature was raised to about 80 ° C. at a rate of about 1 ° C./min. Ethyl acetate was distilled off from the mixture at about 80 ° C. for about 120 minutes. The mixture was cooled to below about 40 ° C. and then screened with a 20 micron sieve. The pH of the mixture was adjusted to about 7 using about 4% aqueous NaOH and centrifuged. The resulting resin contains about 35.3% by weight solids in water and the particles have a volume average diameter of about 122 nanometers measured with a MICROTRAC® UPA150 particle size analyzer from HONEYWELL. Was.

In a 2 liter glass reactor equipped with an overhead stirrer and heating mantle, about 183.25 grams of the above amorphous resin emulsion and about 104.03 grams of the unsaturated crystalline polyester resin emulsion of Example 1 ( About 16.15% by weight of crystalline resin). About 41.82 grams of Al ₂ (SO ₄ ) ₃ solution (1% by weight) was added as a flocculant while homogenizing. Subsequently, the mixture was agglomerated by heating to about 46.2 ° C. with stirring at about 300 rpm. Monitor the particle size with a Coulter counter until the volume average particle size of the core particles is 4.59 μm and the GSD is about 1.25, then add about 85.52 grams of the above amorphous resin emulsion as a shell As a result, core-shell structured particles having an average particle size of about 6.48 microns and a GSD of about 1.23 were obtained. Thereafter, the pH of the reaction slurry is adjusted to about 7.2 using about 1.615 grams of ethylenediaminetetraacetic acid (EDTA) (about 39 wt%) and NaOH (about 4 wt%) to increase toner growth. Frozen.

  After freezing, the reaction mixture was heated to about 69.9 ° C. and the pH was lowered to about 5.97 for fusing. After fusing, the toner was quenched to obtain particles having a final particle size of about 5.90 microns, a GSD of about 1.25, and a roundness of about 0.960. The toner slurry was then cooled to room temperature, separated through a sieve (through a 25 micron sieve), filtered, washed and lyophilized.

Example 2-4
A toner was prepared using about 0.2 wt% IR absorber. An emulsion was prepared containing about 99.8 wt% amorphous resin XP777 available from Reichold Chemicals and about 0.2 wt% IR absorber. About 125 grams of amorphous resin XP777, about 0.24 grams of IR absorber (NK-2911 or NK-4680 (manufactured by Hayashibara Biochemical Laboratories)) or EPOLIGHT ™, a platinum-containing dye 4113 (manufactured by EPOLIN)) and dissolved in a 2 liter beaker containing about 900 grams of ethyl acetate. The mixture was stirred at room temperature at about 300 revolutions per minute to dissolve the resin and IR absorber in ethyl acetate. About 2.56 grams of sodium bicarbonate was weighed and added to a 3 liter Pyrex glass flask reactor containing about 700 grams of deionized water. Homogenization of the aqueous solution in a 3 liter glass flask reactor was initiated using an IKA Ultra Turrax T50 homogenizer operating at about 4,000 revolutions per minute. While continuing to homogenize the mixture, the resin solution was slowly poured into the aqueous solution and the homogenizer speed was increased to about 8,000 revolutions per minute, and at this condition, homogenization was carried out for 30 minutes. Once homogenization was complete, the glass flask reactor and its contents were placed in a heating mantle and connected to a distillation apparatus. The mixture was stirred at about 275 revolutions per minute, the temperature of the mixture was increased to about 80 ° C. at a rate of about 1 ° C. per minute, and ethyl acetate was distilled off from the mixture.

Stirring of the mixture was continued at about 80 ° C. for about 180 minutes, followed by cooling to room temperature at about 2 ° C. per minute. The product was sieved through a 25 micron sieve. The resulting resin emulsion contained about 19.61 wt% solids in water with an average particle size of about 135 nm to 200 nm. A toner was prepared using the IR / amorphous resin emulsion described above as follows. About 367.16 grams of the above emulsion containing the amorphous resin and IR absorber was added to a 2 liter glass reactor equipped with an overhead stirrer and heating mantle. In addition, about 48 grams of the unsaturated crystalline polyester resin of Example 1 was added. About 35.84 grams of Al ₂ (SO ₄ ) ₃ solution (about 1% by weight) was added as a flocculant while homogenizing. Subsequently, the mixture was heated to about 40.8 ° C. and agglomerated while stirring at about 260 rpm. The particle size was monitored with a Coulter counter until the volume average particle size of the core particles was about 4.54 μm and the GSD was about 1.21.

  Next, about 171.34 grams of the amorphous resin and IR absorber emulsion described above are added to form a shell, and a core-shell structure having an average particle size of about 5.77 microns and a GSD of about 1.22. Particles were obtained. The pH of the reaction slurry was then adjusted to about 7.25 using about 1.39 grams of EDTA (about 39 wt%) and NaOH (about 4 wt%) to freeze toner growth.

  After freezing, the reaction mixture was heated to about 69 ° C. and the pH was lowered to about 5.9 for fusing. After fusing, the toner was cooled rapidly. The toner slurry was then cooled to room temperature, separated through a sieve (25 micron sieve), filtered, washed and lyophilized.

A summary of the IR absorbers used to produce these toners and the resulting final particle size and roundness is shown in Table 1 below.
Table 1
Toner containing amorphous resin, crystalline resin, and IR absorber

  UV-Vis-NIR spectra of some of the above components and compositions were measured using a Vary Inc. Cary 5000 spectrometer.

  FIG. 1 is a UV-vis-NIR spectrum obtained for the NK-2911 IR absorber, which shows that the IR absorber has a maximum absorption at about 831 nm when dissolved in MeOH. FIG. 2 is a UV-vis-NIR spectrum of an amorphous resin in THF, which shows absorption only in the UV region. FIG. 3 is a UV-vis-NIR spectrum of an amorphous resin emulsified with 0.2 wt% NK-2911 IR absorber. The mixture was dissolved in ethyl acetate and had a peak at 836 nm. The peak from about 200 nm to about 320 nm was absorption of amorphous resin.

Fixing Results A non-fixed toner image was created using a Xerox DC12 printer (S / N = FU0-025042) and imaged on 120 gsm DCEG (Digital Color Elite Gloss, P / N3R11450) coated paper. A more uniform image quality was obtained using a toner mass area (TMA) slightly higher than the nominal value (0.48 mg / cm ² ). The developer loading was 35 grams for toner and 365 grams for Xerox DC-12 carrier. A good quality image was created using this EA toner. The target image used in these tests was a solid area arranged near the center of the page.

表３
カラー特性（デルタE2000）

また、本発明は以下の事項として捉えることもできる。
〔１〕少なくとも１つの非晶質樹脂と、
少なくとも１つの赤外線吸収体と、
少なくとも１つの結晶性樹脂と、
随意の着色剤と、
随意のワックスと、
を含み、
前記少なくとも１つの赤外線吸収体は、約７００ｎｍから約８５０ｎｍまでの波長において最大吸光度を有することを特徴とするトナー。
〔２〕前記トナーは、乳化凝集トナーを含み、
前記トナーを含む粒子は、随意的に前記少なくとも１つの赤外線吸収体と組み合わせた前記少なくとも１つの非晶質樹脂を含むシェルをさらに含み、
前記赤外線吸収体は、シアニン、プラチナ含有染料、及びこれらの組み合わせの群から選択され、約３８０ｎｍから約７００ｎｍまでの波長では光を吸収せず、かつ、前記トナーは非接触定着に使用され、
前記トナーを含む粒子の直径は、約２．７５ミクロンから約１０ミクロンまでであり、約０．９３から約０．９９までの真円度を有し、
前記トナーは、約２０ｇｇｕから約１００ｇｇｕまでの光沢度を有し、母体トナーの電荷対質量比は、約−１０μＣ／ｇから約−４０μＣ／ｇまでであることを特徴とする、前記〔１〕に記載のトナー。
〔３〕少なくとも１つの非晶質ポリエステル樹脂と、
少なくとも１つの赤外線吸収体と、
少なくとも１つの結晶性ポリエステル樹脂と、
随意の着色剤と、
随意のワックスと、
を含み、
前記少なくとも１つの赤外線吸収体は、約７００ｎｍから約８５０ｎｍまでの波長において光の最大吸収率を有し、約３８０ｎｍから約７００ｎｍまでの波長における光は吸収しないことを特徴とするトナー。
〔４〕少なくとも１つの加熱装置と、
トナー供給源と、
随意の接触定着器と
約７５０ｎｍから約２５００ｎｍまでの波長において動作する赤外光源を備えた非接触定着器と、
基材予熱器と、
画像支持部材予熱器と、
注入器と、
を含み、
前記トナーは、少なくとも１つの非晶質樹脂と、少なくとも１つの赤外線吸収体と、少なくとも１つの結晶性ポリエステル樹脂と、随意の着色剤と、随意のワックスとを含み、 前記少なくとも１つの赤外線吸収体は、約７００ｎｍから約８５０ｎｍまでの波長において最大吸光率を有し、かつ、約３８０ｎｍから約７００ｎｍまでの波長においては光を吸収しないことを特徴とする印刷装置。 Non-contact fixing was performed using an IR heating module mounted above the belt carrier system. A Heraerus IR radiator with three twin tube lamps with a short wavelength of 1.2 microns to 1.4 microns and 5.4 kW was used for this test. Along with the gloss measurement, print sampling was performed under an IR emission lamp at various transport speeds (mm / second (mm / s)) listed in Table 2 below. The color results showing the color difference (ΔE2000) for the sample without IR absorber for the test run are summarized in Table 3 below.
Table 2
Average print gloss at various speeds

Table 3
Color characteristics (Delta E2000)

Moreover, this invention can also be grasped | ascertained as the following matters.
[1] at least one amorphous resin;
At least one infrared absorber;
At least one crystalline resin;
Optional colorants,
With optional wax,
Including
The toner wherein the at least one infrared absorber has a maximum absorbance at a wavelength from about 700 nm to about 850 nm.
[2] The toner includes an emulsion aggregation toner,
The toner-containing particles further comprise a shell comprising the at least one amorphous resin optionally in combination with the at least one infrared absorber;
The infrared absorber is selected from the group of cyanine, platinum-containing dyes, and combinations thereof, does not absorb light at wavelengths from about 380 nm to about 700 nm, and the toner is used for non-contact fixing,
The particles comprising the toner have a diameter of about 2.75 microns to about 10 microns, and a roundness of about 0.93 to about 0.99,
The toner has a glossiness of about 20 ggu to about 100 ggu, and the charge-to-mass ratio of the base toner is about −10 μC / g to about −40 μC / g [1] The toner described in 1.
[3] at least one amorphous polyester resin;
At least one infrared absorber;
At least one crystalline polyester resin;
Optional colorants,
With optional wax,
Including
The toner wherein the at least one infrared absorber has a maximum light absorption at a wavelength of about 700 nm to about 850 nm and does not absorb light at a wavelength of about 380 nm to about 700 nm.
[4] at least one heating device;
A toner supply source;
With optional contact fuser
A non-contact fuser comprising an infrared light source operating at a wavelength from about 750 nm to about 2500 nm;
A substrate preheater;
An image support member preheater;
An injector,
Including
The toner includes at least one amorphous resin, at least one infrared absorber, at least one crystalline polyester resin, an optional colorant, and an optional wax, and the at least one infrared absorber. Has a maximum absorbance at wavelengths from about 700 nm to about 850 nm and does not absorb light at wavelengths from about 380 nm to about 700 nm.

Claims (3)

Including core and shell,
The core is
At least one amorphous resin;
At least one infrared absorber;
At least one crystalline resin derived from dodecanedioic acid, ethylene glycol, and fumaric acid ;
Optional colorants,
With optional wax,
Including
The shell includes at least one amorphous resin combined with at least one infrared absorber;
The toner according to claim 1, wherein the at least one infrared absorber has a maximum absorbance at a wavelength of 700 nm to 850 nm. The toner includes an emulsion aggregation toner,
The infrared absorber is selected from the group of cyanine, platinum-containing dyes, and combinations thereof, and does not absorb light at wavelengths from 380 nm to 700 nm, and the toner is used for non-contact fixing,
The toner according to claim 1, wherein the toner-containing particles have a diameter of 2.75 to 10 microns and a roundness of 0.93 to 0.99. Including core and shell,
The core is
At least one amorphous polyester resin;
At least one infrared absorber;
At least one crystalline polyester resin derived from dodecanedioic acid, ethylene glycol, and fumaric acid ;
Optional colorants,
With optional wax,
Including
The shell includes at least one amorphous resin combined with at least one infrared absorber;
The toner according to claim 1, wherein the at least one infrared absorber has a maximum light absorption at a wavelength of 700 nm to 850 nm and does not absorb light at a wavelength of 380 nm to 700 nm.

Images